EP0508038A1 - Sulfosuccinates of esters of citric acid, of fatty alcohols and polyglycolic ethers, process for their preparation and their use - Google Patents

Abstract

The invention relates to polyglycol ether sulphosuccinates of fatty alcohol esters of citric acid of the general formula (I) <IMAGE> in which   R is H or -CH3, which can be identical or different,   R<1> is <IMAGE>   R<2> is R<1> or H or   R<3> is an alkyl or acyl radical having 8-22 C atoms, which is optionally substituted and/or contains multiple bonds,   a and b are identical or different and can be 0-5, where a+b is >/= 1 and   c is 0-15 and   x<+> is H<+> or a cation, their preparation and their use.

Description

The invention relates to new citric acid fatty alcohol ester polyglycol ether sulfosuccinates, processes for their preparation and their use as cleaning agents and for cosmetic preparations.

Cosmetic preparations, in particular those which fall into the field of hair and body cleaning, such as shower baths, foam baths, hair shampoos, liquid soaps, contain as cleaning components mainly anionic surfactants such as carboxylates, alkyl sulfates and alkyl ether sulfates, sulfosuccinates.

These preparations are intended to clean the skin surface, preferably only the film adhering to it, which can consist of body exudates such as sweat and fats, skin flakes or deposited dirt from the environment. Under no circumstances should the cleaning agents leach the skin, irritate it or impair its natural function.

However, since the preparations, when used frequently - in the last few years almost every day - can irritate the skin, so-called mild surfactants, such as betaines, protein derivatives, ampholytes, alkyl ether carboxylates and sulfosuccinates, are often used to improve skin and eye mucosa tolerance.

Particularly for baby care products and baby shampoos, special emphasis is placed on extremely low levels of irritating substances on the skin and mucous membranes of the eyes. The conventional Because of the excellent cleaning and foaming properties of the anionic surfactants used, the irritating effect of the known mild co-surfactants can be largely mitigated, but in practice improvements are still required, particularly with regard to compatibility with the eye mucosa.

In high concentrations or alone, the mild surfactants are largely irritation-free, but then show no practical foaming and cleaning properties and unsatisfactory viscosities.

Another criterion for the usefulness of the surface-active substances is their toxicity. The toxicity lies in the surfactants themselves or in their products that result from their interaction with the components of the formulation.

For example, the fatty acid alkanolamides which have been used with pleasure up to now because of their advantageous application technology and skin care properties have recently been reluctantly used in cosmetic preparations, since the remaining free diethanolamine content during production cannot be ruled out and can therefore give rise to nitrosamine formation (EP-A- 0 306 843). N-nitrosamines are carcinogenic in animal experiments.

Due to the increased environmental awareness, products are still required that are based on natural renewable raw materials, have no toxicity and can be quickly and completely broken down in the municipal sewage treatment plants without toxic intermediate products.

The products based on citric acid, such as the mono- and / or difatty acid ester alkoxylates based on glycerin, which have been introduced in practice, have low toxicities and are mild products which do not irritate the skin, but which do not meet practical requirements in terms of their cleaning effect or solubility .

The object of the present invention is to overcome these disadvantages of the prior art and to provide mild, skin-friendly cleaning agents for household and industry and cosmetic preparations, in particular those which fall into the field of hair and body cleaning.

worin

R =

gleich oder verschieden H oder -CH₃

R¹ =

R² =

R¹ oder H oder R³

R³ =

ein gegebenenfalls substituierter und/oder Mehrfachbindungen enthaltender Alkyl- oder Acylrest mit 8 - 22 C-Atomen, vorzugsweise 12 - 18 C-Atomen

a,b =

gleich oder verschieden 0 - 5, vorzugsweise 1 - 3, sein kann, wobei a+b ≧1, vorzugsweise ≧2, insbesondere im Bereich von 2 - 5, liegt und

c =

0 - 15, vorzugsweise 1 - 10, insbesondere

x⁺ =

H⁺ oder ein Kation ist.

This object is achieved by the sulfosuccinates based on citric acid and containing alkoxylated ester groups. The invention relates to citric acid fatty alcohol ester polyglycol ether sulfosuccinates of the general formula (1)

wherein

R =

the same or different H or -CH₃

R¹ =

R² =

R¹ or H or R³

R³ =

an optionally substituted and / or containing multiple bonds alkyl or Acyl radical with 8-22 carbon atoms, preferably 12-18 carbon atoms

a, b =

may be identical or different 0-5, preferably 1-3, where a + b ≧ 1, preferably ≧ 2, in particular in the range 2-5, and

c =

0-15, preferably 1-10, in particular

x⁺ =

H⁺ or a cation.

Another object of the invention is a process for the preparation of compounds of general formula (1).

The invention further relates to aqueous hair cleaning and care products, dishwashing detergents, all-purpose cleaners, neutral cleaners, skin care and cleaning products, which are characterized in that they contain 1 to 10, preferably 2 to 8 parts by weight of at least one of the compounds of the general formula (1 ), defined amounts of at least one surfactant from the group of nonionic, amphoteric, zwitterionic and ionic surfactants, preferably 0.1 to 30 parts by weight, optionally 0.1 to 15 parts by weight of one of the customary agents from the group of additives - And auxiliaries, thickeners, fragrances, preservatives, dyes, plant extracts and optionally ad 100 water.

Further objects of the invention are characterized by the claims.

A starting material for the preparation of the compounds of the general formula (1) according to the invention is natural or synthetic citric acid. Depending on the requirements of the end product, highly purified quality or commercially available goods of technical purity can be used.

In a first step, the citric acid can be reacted with one or two moles of fatty alcohol or fatty alcohol alkoxylate according to the known methods to give the ester (US Pat. No. 2,076,111, US Pat. No. 3,948,976, EP 0 199 131). The monoesters are preferred according to the invention.

The alcohols used are the monofunctional fatty alcohols with 8-22 C atoms - preferably the naturally occurring ones - and the fatty alcohols which can be prepared from the synthetic or natural fatty acids by known processes, such as lauryl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol, linolyl alcohol , Tallow alcohol and the alcohols based on natural coconut fatty acids.

Synthetic alcohols, such as. B. the compounds prepared after the oxo synthesis or after the Guerbet reaction can also be used.

The alcohols can be used as such or in the form of the alcohols alkoxylated, preferably ethoxylated and / or propoxylated therefrom by known processes, containing at least one ether group.

Alkoxylation products with C = 1-15, preferably 1-10 and 11 alkoxy units / mole of fatty alcohol (US Pat. No. 4,866,203 and the references cited therein) are preferred according to the invention.

Instead of the fatty alcohol alkoxylates, the fatty acids alkoxylated, preferably ethoxylated and / or propoxylated, by known processes can also be used (EP-A-0 334 482).

The degrees of alkoxylation correspond to those of the fatty alcohol alkoxylates. In these products, R³ of general formula 1 is an acyl radical.

The fatty acids used are the monobasic acids with 8-22 carbon atoms - preferably those which occur naturally - such as lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, coconut fatty acid or mixtures thereof.

These esters are reacted in a second step according to methods known per se (J. Am. Oil Chemist's Soc., 1956, 33, 571, EP-A-0 334 482) with alkylene oxides such as, in particular, ethylene oxide and propylene oxide to give the polyglycol ether esters, in which statistical averages 0 - 5, preferably 1 - 3, mol of alkylene oxide per carboxyl group. It was found that the products according to the invention with a total of (a + b of the general formula 1) ≧ 1, preferably ≧ 2 mol of alkylene oxide give excellent results. In products which are particularly preferred according to the invention, a + b is between 2 and 5.

The citric acid can also be alkoxylated in the first stage by the known processes mentioned above and reacted in the second stage with 1 or 2 moles of fatty acid to give the fatty acid ester, where R³ is also an acyl radical and a + b + c = 1-25, preferably 5-15 and in particular 3-5.

The reaction to the sulfosuccinate takes place with maleic anhydride and subsequent sulfonation with sodium sulfite according to methods known per se (DE-OS 2 700 072).

Here, per mole of hydroxyl group to be reacted is stirred with one mole of maleic anhydride at 60-80 ° C. until the anhydride has reacted completely. The maleic acid half-ester is then placed in an aqueous sodium sulfite solution (1 equivalent of sulfite per equivalent of half-ester) and sulfonated at 60-80 ° C. until the sulfite has reacted completely. Then the aqueous product is adjusted to pH neutral.

In general, the process according to the invention is carried out such that in the first stage the citric acid monoesters are esterified with the fatty alcohol or the fatty alcohol alkoxylate, optionally with the use of an esterification catalyst, at 140-160 ° C. with removal of the water of reaction, in the second stage in the presence of a basic catalyst at 80 - 150 ° C and 1 - 10 bar with alkylene oxide to form the alkoxylate, which is added in the third stage by adding maleic anhydride at 60 - 80 ° C to the half ester and in the last stage at 60 - 80 ° C with aqueous sodium sulfite solution to the salt corresponding sulfonic acid is implemented.

The compounds according to the invention are represented in idealized form by the general formula (1). In addition to the specified monofatty acid esters or difatty acid esters, the technical mixtures also contain small amounts Proportions of the higher esters and the degrees of alkoxylation given are statistical averages.

Cleaning is not required for the use according to the invention, that is to say the technical mixtures can be used directly as such.

The mixtures according to the invention for cleaning purposes and cosmetics are generally present as aqueous agents or as aqueous alcoholic solutions, creams, emulsions, gels and can also contain the customary auxiliaries and additives which are required for the production of cleaning agents and cosmetic preparations in the area of hair and body cleaning, i.e. for shower baths, foam baths, shampoos, liquid soaps, baby care and washing agents as well as for mild cleaning agents such as dishwashing detergents, all-purpose cleaners or neutral cleaners which are common for manual use.

The surfactants, fragrances, preservatives, dyes, plant extracts or other cosmetic additives customary in these fields can also be used for cosmetic applications.

In addition to the known betaines, amphoteric and nonionic compounds for the cleaning formulations, the surfactants in particular include the anionic surfactants such as carboxylates, alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkyl ether sulfonates and alkyl sulfosuccinates. According to the invention, alkylamidobetaines such as REWOTERIC ^{R 1} ) AM B 13 and AM B 14, carboxyglycinates such as REWOTERIC ^R AM 2 C NM, carboxypropionates like REWOTERIC ^R AM KSF 40, sulfobetaines like REWOTERIC ^R AM CAS, anionic surfactants like ether sulfates REWOPOL ^{R 2)} NL 3, ether carboxylates like REWOPOL ^R CLN 100, sulfosuccinates like REWOPOL ^R SB FA 30, REWOPOL ^R SBZ, REWODERM ^{R 3)} SPS, non-ionic surfactants such as glycerol fatty acid ester ethoxylates such as REWODERM ^R ES 90, glycerol monostearate such as REWOMUL ^{R 4)} MG, cetyl alcohol ( ¹⁾ , ²⁾ , ³⁾ , ⁴⁾ = trademark of REWO Chemische Werke GmbH, Steinau on the street).

In addition to the compounds according to the invention, which are present in amounts of 1-10 parts by weight, in particular 2-8 parts by weight, for shampoos and 1-7 parts by weight, preferably 1-5 parts by weight, for creams and 1 - 5, preferably 1.5 - 3 parts by weight for detergents, the other surfactants for shampoos are usually used in amounts of 1 - 20 parts by weight, preferably 5 - 15 parts by weight, for the creams in Amounts of 1 to 10 parts by weight, preferably 2 to 5 parts by weight, are also used.

1-8 parts by weight of the compounds customary in this field, such as glycerol fatty acid ester ethoxylates, fatty alcohol ethoxylates, fatty acid alkylolamides and the customary alkali metal, alkaline earth metal and ammonium salts, which are soluble in water at 20 ° C. in amounts of at least 1% by weight are used as thickeners are used, in particular NaCl, NH₄Cl.

The analytical values given in the examples below are determined using the following methods which are generally customary in this field:

Acid number (SZ)

The acid number is a measure of the free acidity of a fat or technical fatty acids and gives the milligrams of potassium hydroxide that are necessary to neutralize 1 gram of substance.

The values are determined according to the DGF standard method C-V4.

Dry matter content

The content is determined by heating and drying at 105 ° C. to constant weight.

Hydroxyl number (OHZ)

The hydroxyl number is used to determine the hydroxyl group content and indicates the number of milligrams of potassium hydroxide required to neutralize the acetic acid consumed by 1 gram of fat in acetylation (mg KOH / g).

Benzavlon-WHAT

The content of wash-active substance (B-WAS) given in the examples below is titrated by the usual two-phase titration with benzalkonium chloride against methylene blue as an indicator (cf. SR Apton, Nature (London) 160, 1967, p. 795).

Preparation of the compounds according to the invention example 1 1.1 esterification

377 g (1.79 mol) of citric acid monohydrate, 723.6 g (1.97 mol) of REWOPAL ^R LA 4 * and 1.3 g of hypophosphorous acid were placed under nitrogen in a reaction vessel equipped with a stirrer, thermometer, a water separator and a cooler , filled.
* = Product and trademark of REWO Chemische Werke GmbH; C _12/14 fatty alcohol ethoxylate with 4 ethylene oxide units (EO) and an OHZ of 153.

The mixture was heated to 140 ° C. under an N₂ atmosphere and with good stirring and kept at this temperature for 2 hours. During this time, almost the theoretical amount of water of reaction distilled off. After the reaction mixture had cooled to 80 ° C., the pressure was slowly reduced to 20 mbar and the reaction was completed at this pressure and 140 ° C.

The reaction product has an acid number of 200.

1.2 Ethoxylation

784 g of citric acid monoesters from Example 1.1 were reacted in portions with 119 g of ethylene oxide after addition of 4 g of alkyldimethylamine at 90 ° C. in an autoclave, so that the pressure was a maximum of 5 bar. Analysis data: Acid number 24.6 mg KOH / g Hydroxyl number 187.3 mg KOH / g

1.3 Half-education

333 g (1.2 mol) of ethoxylate from Example 1.2 were mixed at 70 - 80 ° C under N₂ with 98 g (1.0 mol) of maleic anhydride and stirred at this temperature for 2 h. The reaction product had the following analytical numbers: Acid number in acetone 148.2 mg KOH / g Acid number in isopropanol 140.2 mg KOH / g

1.4 sulfation

350 g of half-ester from Example 1.3 were slowly added dropwise at this temperature to a solution of 108 g (1.0 mol) of sodium sulfite in 680 g of water at 60-70 ° C. The solution had the following analytical data: Dry residue 40.4% Benzavlon-WHAT 34.3% pH value (5%) 6.1

Example 2 2.1 esterification

210 g (1 mol) of citric acid monohydrate, 507 g (1.1 mol) of REWOPAL ^R LA 6 * and 1.3 g of hypophosphorous acid were introduced under N₂ into a reaction vessel equipped with a stirrer, thermometer, a water separator and a cooler.
* = Product and trademark of REWO Chemische Werke GmbH; C _12/14 fatty alcohol ethoxylate with 6 ethylene oxide units (EO) and an OHZ of 130.

The mixture was heated to 140 ° C. under a nitrogen atmosphere and with good stirring and held at this temperature for 2 hours. During this time, almost the theoretical amount of water of reaction distilled off. The reaction mixture was allowed to cool to 80 ° C and a vacuum of 20 mbar was applied to complete the reaction. The acid number of the end product was 173.

2.2 ethoxylation

After the addition of 3 g of alkyldimethylamine at 90 ° C. in an autoclave, 610 g of citric acid monoesters from Example 2.1 were reacted in portions with 116 g of ethylene oxide, so that the pressure was a maximum of 5 bar. Analysis data: Acid number 6.7 mg KOH / g Hydroxyl number 185 mg KOH / g

2.3 Half-education

363 g (1.2 mol) of ethoxylate from Example 2.2 were mixed at 70 - 80 ° C under N₂ with 98 g (1 mol) of maleic anhydride and stirred at this temperature for 2 h. The reaction product had the following analytical numbers: Acid number in acetone 150 mg KOH / g Acid number in isopropanol 137 mg KOH / g

2.4 sulfation

350 g of half-ester from Example 2.3 were slowly added dropwise at this temperature to a solution of 101 g (1 mol) of sodium sulfite in 680 g of water at 60-70 ° C. The solution had the following analytical data: Dry residue 39.7% Benzavlon-WHAT 28.4% pH value (5%) 6.3

Example 3 3.1 esterification

141 g (0.67 mol) of citric acid monohydrate, 470 g (0.73 mol) of REWOPAL ^R LA 10 * and 1 g of hypophosphorous acid were introduced under N₂ into a reaction vessel equipped with a stirrer, thermometer, a water separator and a cooler.
* = Product and trademark of REWO Chemische Werke GmbH; C _12/14 fatty alcohol ethoxylate with 10 ethylene oxide units (EO) and an OHZ of 90.

The mixture was heated to 140 ° C. under a nitrogen atmosphere and with good stirring and held at this temperature for 2 hours. During this time, almost the theoretical amount of water of reaction distilled off (acid number of the product: 121). The reaction mixture was allowed to cool to 80 ° C and a vacuum of 20 mbar was applied to complete the reaction. The acid number of the end product was 113.

3.2 ethoxylation

513 g of citric acid monoesters from Example 3.1 were added in portions with 60 g of ethylene oxide after addition of 2.6 g of alkyldimethylamine at 90 ° C. in an autoclave, so that the pressure was a maximum of 5 bar. Analysis data: Acid number 2.7 mg KOH / g Hydroxyl number 108 mg KOH / g

3.3 Half-education

478 g (0.9 mol) of ethoxylate from Example 3.2 were mixed at 70 - 80 ° C under N₂ with 75 g (0.8 mol) of maleic anhydride and stirred at this temperature for 2 h. The reaction product had the following analytical numbers: Acid number in acetone 89.3 mg KOH / g Acid number in isopropanol 82.8 mg KOH / g

3.4 sulfation

480 g of half-ester from Example 3.3 were slowly added dropwise at a temperature of 60-70 ° C. to a solution of 89 g (0.8 mol) of sodium sulfite in 850 g of water. The solution had the following analytical data: Dry residue 39.2% Benzavlon-WHAT 28.9% pH value (5%) 6.1

Example 4 4.1 esterification

225 g (1.1 mol) of citric acid monohydrate, 506 g (1.1 mol) of REWOPAL ^R TA 6 * and 0.7 g of hypophosphorous acid were introduced under N₂ into a reaction vessel equipped with a stirrer, thermometer, a water separator and a cooler.
* = Product and trademark of REWO Chemische Werke GmbH; C _16/18 fatty alcohol ethoxylate with 6 ethylene oxide units (EO) and an OHZ of 120.

The mixture was heated to 140 ° C. under a nitrogen atmosphere and with good stirring and kept at this temperature for 4 hours. During this time, almost the theoretical amount of water of reaction distilled off. The reaction solution was allowed to cool to 90 ° C and a vacuum of 20 mbar was applied to complete the reaction. The acid number of the end product was 173.

4.2 Ethoxylation

635 g of citric acid monoesters from Example 4.1 were reacted in portions with 97 g of ethylene oxide after addition of 3 g of alkyldimethylamine at 90 ° C. in an autoclave, so that the pressure was a maximum of 5 bar. Analysis data: Acid number 26 mg KOH / g Hydroxyl number 138 mg KOH / g

4.3 Half-education

293 g (0.7 mol) of ethoxylate from Example 4.2 were mixed at 70 - 80 ° C under N₂ with 59 g (0.6 mol) of maleic anhydride and stirred at this temperature for 2 h. The reaction product had the following analytical numbers: Acid number in acetone 133 mg KOH / g Acid number in isopropanol 122 mg KOH / g

4.4 Sulfation

293 g of half-ester from Example 4.3 were slowly added dropwise at 60-70 ° C. to a solution of 66 g (0.6 mol) of sodium sulfite in 535 g of water at this temperature. The solution had the following analytical data: Dry residue 39.4% Benzavlon-WHAT 28.9% pH value (5%) 6.4

Example 5 5.1 esterification

210 g (1 mol) of citric acid monohydrate, 735 g (2 mol) of REWOPAL ^R LA 4 * and 1 g of hypophosphorous acid were added N₂ filled into a reaction vessel equipped with a stirrer, thermometer, a water separator and a cooler.
* = Product and trademark of REWO Chemische Werke GmbH; C _12/14 fatty alcohol ethoxylate with 4 ethylene oxide units (EO) and an OHZ of 153.

The mixture was heated to 140 ° C. under a nitrogen atmosphere and with good stirring and held at this temperature for 2 hours. During this time, almost the theoretical amount of water of reaction distilled off. The reaction mixture was allowed to cool to 80 ° C and a vacuum of 20 mbar was applied to complete the reaction. The acid number of the end product was 68.

5.2 Ethoxylation

837 g of citric acid monoesters from Example 5.1 were added in portions with 45 g of ethylene oxide after addition of 4.1 g of alkyldimethylamine at 90 ° C. in an autoclave, so that the pressure was a maximum of 5 bar. Analysis data: Acid number 10.6 mg KOH / g Hydroxyl number 92.4 mg KOH / g

5.3 Half-formation

364 g (0.6 mol) of ethoxylate from Example 5.2 were mixed at 70 - 80 ° C under N₂ with 59 g (0.6 mol) of maleic anhydride and stirred at this temperature for 2 h. The reaction product had the following analytical numbers: Acid number in acetone 103 mg KOH / g Acid number in isopropanol 92 mg KOH / g.

5.4 Sulfation

352 g of half-ester from Example 5.3 were slowly added dropwise at a temperature of 60-70 ° C. to a solution of 66 g (0.6 mol) of sodium sulfite in 625 g of water. The solution had the following analytical data: Dry residue 39.4% Benzavlon-WHAT 27.8% pH value (5%) 6.9

Cosmetic formulations

The formulations below can be prepared by simply stirring the formulation ingredients into water.

All recipes are given in percent by weight based on solids.

Explanation of the surfactants used according to the CTFA name:

1 =

Disodium PEG-4 Cocoamido MIPA sulfosuccinate

2 =

Disodium lauroamphodiacetate
(and) Sodium Lauryl Sulfate
(and) Hexylene Glycol

3 =

Cocoamidopropyl hydroxysultaine

4 =

Ricinoleamidopropyltrimonium methosulfate

5 =

PEG-200 Glyceryl Tallowate mod.

6 =

Disodium Laureth Sulfosuccinate

7 =

Sodium Laureth Sulfate

8 =

Cocoamidopropyl betaines

9 =

PEG-200 Glyceryl Tallowate

10 =

Disodium cocoamphodiacetate

11 =

PEG-80 Glyceryl Tallowate

12 =

Cocoamidopropyl betaines

13 =

Glyceryl stearate

14 =

Laureth-6

Analysis methods:

Viskosität:

Brookfiled Rotationsviskosimeter (Becher und Spindel) gemessen bei 20 °C nach den Angaben des Geräteherstellers.

Calcium hardness compatibility: DIN 53 905
Skin tolerance (zein test):
Götte, Ernst, Chem. Phys. Appl. Surface Active Subst. Proc. Int. Congr. 4 (1964) 83-90:
<200 mgN / 100 ml = not irritating
200-400 mgN / 100 ml = slightly irritating
> 400 mgN / 100 ml = irritating
Surface tension:
Dr. R. Hensch; Fette, Seifen, Anstrichmittel, 72 (1970), pp. 969-977

Viscosity:

Brookfiled rotary viscometer (cup and spindle) measured at 20 ° C according to the device manufacturer's instructions.

Determination of the foaming power according to Ross Miles based on DIN 53902 Part 2 with the modification that the following dimensions and quantities were used: Inner diameter of the outlet nozzle: 3.5 mm Fall height of the sample solution: 940 mm Amount of sample solution presented: 50 ml Amount of incoming sample solution: 200 ml Measuring temperature 40 ° C solvent demineralised water

Test recipe: shower bath

• Anschäumvermögen
• Hautgefühl
• Hautgefühl der abgetrockneten Haut

The examples according to the invention were evaluated in the test formulation by a test panel of 20 people (female and male)

• Foaming power
• Skin feeling
• Dry skin feeling

Skin tolerance: Reduction of the zein values in the recipe Table 4.

Table 3 Recipe 1 2nd 3rd Example 1.4 - 4th - Example 3.4 - - 4th REWOPOL ^R SB Z ¹⁾ 4th - - REWOTERIC ^R AM G 30 ²⁾ 10.5 10.5 10.5 REWOTERIC ^R AM GAS ³⁾ 3rd 3rd 3rd REWOQUAT ^R RTM 50 ⁴⁾ 1 1 1 REWODERM ^R Li S 75 ⁵⁾ 2.3 2.3 2.3 demin. water ad 100 ad 100 ad 100 pH adjusted with citric acid 6.5 6.5 6.5 Viscosity [mPas] 3000 3000 ^∼ 2500 Foaming capacity [mm] 195/185 205/195 200/195 Foaming power ^A) Good Good Good Foam structure ^A) fine bubbles creamy, fine-bubble creamy, fine-bubble Skin feeling, wet skin ^A) relatively smooth smooth smooth Skin feeling, dry skin ^A) relatively smooth smooth smooth ^A) = The evaluation was carried out according to a graded rating system, whereby the above-mentioned evaluation reflects the arithmetic mean

Test formula: hair shampoo

• Kämmbarkeit
• Volumen des Haares und Sitz der Frisur bewertet worden.

Tabelle 5 Rezeptur 1 2 3 Beispiel 1.4 - 3 - Beispiel 2.4 - - 3 REWOPOL^R NL 3-28 ⁷⁾ 8 6 6 REWOTERIC^R AM B 13 ⁸⁾ 5 4 4 REWODERM^R Li 420-70 ⁹⁾ 2,1 2,1 2,1 demin. Wasser ad 100 ad 100 ad 100 pH-Wert, mit Citronensäure eingestellt 6,5 6,5 6,5 Kämmbarkeit 3 5-6 5-6 Volumen des Haares Sitz der Frisur 3-4 6 6 Viskosität [mPas] ^∼3000 ^∼12000 ^∼12000 Schaumhöhe [mm] 195/185 195/185 195/185 The examples according to the invention are based on the recipe of 10 test persons experienced in use

• Combability
• Volume of hair and fit of hairstyle have been assessed.

Table 5 Recipe 1 2nd 3rd Example 1.4 - 3rd - Example 2.4 - - 3rd REWOPOL ^R NL 3-28 ⁷⁾ 8th 6 6 REWOTERIC ^R AM B 13 ⁸⁾ 5 4th 4th REWODERM ^R Li 420-70 ⁹⁾ 2.1 2.1 2.1 demin. water ad 100 ad 100 ad 100 pH adjusted with citric acid 6.5 6.5 6.5 Combability 3rd 5-6 5-6 Volume of hair fit the hairstyle 3-4 6 6 Viscosity [mPas] ^∼ 3000 ^∼ 12000 ^∼ 12000 Foam height [mm] 195/185 195/185 195/185

Combability assessment:

1 - 3:

difficult to comb through, the hair offers considerable resistance to the combing process

4 - 7:

the hair is relatively easy to comb, combing resistance is reduced, depending on the hair type, sufficient for a conditioning shampoo

8-10:

reserved for the subsequent post-treatment by so-called hair rinse agents

Assessment of hair volume and fit of the hairstyle

1 - 3:

the hair is dry or straw, bad fit of the hairstyle

4 - 7:

the hair is soft and full, while the hairstyle fits well

8-10:

the hair is soft and smooth, but too loose, so the hairstyle does not fit well.

The evaluation was carried out according to a graded point system, the evaluation given above representing the arithmetic mean.

Test formulation: Baby Shampoo and hair and body shampoo for sensitive skin

Table 6 Recipe 1 2nd 3rd Example 1.4 - 3rd - Example 2.4 - - 3rd REWOTERIC ^R AM 2C NM ¹⁰⁾ 3.5 3.5 3.5 REWOTERIC ^R) AM B 13 ⁸⁾ 7 7 7 REWOPOL ^R) NL 3-28 ⁷⁾ 7.5 4.5 4.5 REWODERM ^R) Li 48-50 ¹¹⁾ 3rd 3rd 3rd demin. water ad 100 ad 100 ad 100 pH adjusted with citric acid 6.5 6.5 6.5 Foam height mm DIN 53 902 part 2 195/185 200/190 200/190 Zein values, mgN / 100 ml (skin tolerance) ^∼ 70 ^∼ 70 ^∼ 70 Foam structure coarse-bubble fine bubbles fine bubbles Skin feeling, wet and dry skin a little rough smooth soft smooth soft

Test recipe: skin cleanser and make-up remover for sensitive skin

Table 7 Recipe 1 2nd 3rd Example 3.4 - - 4th Example 1.4 - 4th - REWOPOL ^R SB FA 30 ⁶⁾ 4th - - REWOTERIC AM B 14 ¹²⁾ 4.5 4.5 4.5 Hydroxyethyl cellulose 0.5 0.5 0.5 demin. water ad 100 ad 100 ad 100 pH adjusted with citric acid 6.5 6.5 6.5 Zein values mgN / 100 ml (skin tolerance) approx. 170 <50 <50

The use of the sulfosuccinates according to the invention in the present formulation results in a cleaning agent which is very well tolerated by the skin, which is evident in the low zein value in comparison to the standard sulfosuccinates REWOPOL ^R SB FA 30.

• gut auf der Haut zu verstreichen
• gut in die Haut einziehend
• die Haut wird glatt und weich, ohne klebrig, fettig zu sein.

Evaluation of the properties on the skin by 10 test persons; more than 80% rated test formulations 3 and 4 as

• to spread well on the skin
• well absorbed into the skin
• the skin becomes smooth and soft without being sticky or greasy.

Comparative recipe 1 is rated the same, recipe 2 is unstable.

Claims (10)

Process for the preparation of the compounds of general formula (1)

wherein R = the same or different H or -CH₃ R¹ =

R² = R¹ or H or R³ R³ = an optionally substituted and / or multiple bond-containing alkyl or acyl radical with 8-22 carbon atoms a, b = may be the same or different 0 - 5, with a + b ≧ 1 and c = 0 - 15 and x⁺ = H⁺ or a cation, characterized in that in the first stage the citric acid monoesters are esterified with the fatty alcohol or the fatty alcohol alkoxylate, optionally with the use of an esterification catalyst, at 140-160 ° C with removal of the water of reaction, this in the second stage in the presence of a basic catalyst at 80-150 ° C and 1 - 10 bar is reacted with alkylene oxide to give the alkoxylate, which is added in a third stage by adding maleic anhydride at 60 - 80 ° C to Half-ester and in the last stage at 60 - 80 ° C with aqueous sodium sulfite solution to the salt of the corresponding sulfonic acid. A process for the preparation of compounds of general formula (1) according to claim 1, characterized in that R = H R1, R2 =

R³ = alkyl radical with 12 - 18 carbon atoms a + b = 2 - 5 c = 1 - 10 and x⁺ = is a cation. A process for the preparation of compounds of general formula (1) according to claim 1, characterized in that a + b + c = 5-15, R³ = acyl radical with 8-18 C atoms from the natural mixture of coconut fatty acids. Process according to claims 1-3, characterized in that the alkoxylates are prepared in the first stage and the esters in the second stage. Containing aqueous hair cleaning and care products a) 1-10 parts by weight of at least one of the compounds of the general formula (1) and b) 1 - 20 parts by weight of at least one surfactant from the group of nonionic amphoteric, zwitterionic, ionic surfactants and optionally c) 0.1-10 parts by weight of thickeners, fragrances, preservatives, dyes, plant extracts and other additives and auxiliaries and d) ad 100 water. Aqueous shower and hair shampoo containing a) 1-10 parts by weight of the compounds of the general formula (1) b) 1 - 20 parts by weight of at least one nonionic, amphoteric, zwitterionic, ionic surfactant and c) 0.1-10 parts by weight of thickeners, fragrances, preservatives, dyes, plant extracts and other additives and auxiliaries and, if appropriate d) ad 100 water. Aqueous dishwashing liquid containing a) 1-10 parts by weight of at least one of the compounds of the general formula (1) and b) 1 - 30 parts by weight of at least one surfactant from the group of nonionic, amphoteric, zwitterionic, ionic surfactants and optionally c) 0.1-10 parts by weight of thickeners, fragrances, preservatives, dyes, plant extracts and other additives and auxiliaries and, if appropriate d) ad 100 water. Skin care products containing a) 1-10 parts by weight of at least one of the compounds of the general formula (1) and b) 1 - 10 parts by weight of at least one surfactant from the group of nonionic, amphoteric, zwitterionic, ionic surfactants and optionally c) 2 - 10 parts by weight of vegetable or mineral oils, ester oils d) 1 - 5 parts by weight of consistency generator e) 0.5 - 5.0 parts by weight of fragrances, dyes, preservatives f) ad 100 water. Containing skin cleanser a) 1-10 parts by weight of at least one of the compounds of the general formula (1) and b) 0.1-20 parts by weight of at least one surfactant from the group of nonionic, amphoteric, zwitterionic, ionic surfactants and optionally c) 0.1-10 parts by weight of thickeners, fragrances, preservatives, dyes, plant extracts and other additives and auxiliaries and, if appropriate d) ad 100 water.